CN114395371B - Composite wave absorber based on tetrazole copper acetate-iron complex derivative and preparation method thereof - Google Patents
Composite wave absorber based on tetrazole copper acetate-iron complex derivative and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of deviceCopper chloride and ferric nitrate are used as metal salts, tetrazole acetic acid is used as an organic ligand, water is used as a solvent, and copper-ferric heteronuclear energetic complex { [ is synthesized under the room temperature condition ] 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n The Fe is decomposed by explosion in a closed reaction kettle and then calcined for 2 hours in nitrogen atmosphere at a certain temperature, thus obtaining Fe 3 O 4 、Fe 4 N、Cu、CuFe 2 O 4 The nano-micron porous composite wave-absorbing material consists of amorphous carbon and graphene. The effective absorption bandwidth is 17.1GHz (0.9-18 GHz) below-10 dB within the range of 0-18GHz and the thickness is 1-10mm, so that the material is a near-full-band wave-absorbing material; when the matching thickness is 1.1 and mm, the maximum reflection loss reaches-40.1 dB at 16.3GHz, and the matching thickness has the potential of being an ultrathin wave-absorbing material. The preparation method has the characteristics of environment friendliness, no toxic by-products, simple preparation process and the like.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a composite wave-absorbing material derived from tetrazole copper-iron acetate complex and a preparation method thereof.
Background
Electromagnetic waves have penetrated into various aspects of human life as carriers of information transmission. With the application and development of radio and radar systems, the problem of electromagnetic wave radiation is more and more serious, and the interference is caused to the normal operation of electronic equipment, so that the safety of military information and the physical and mental health of human beings are more seriously threatened. In daily life, the main electromagnetic pollution comes from broadcast transmitting systems, radio frequencies and some household appliances, and the working frequencies of the devices are almost in the low frequency range of 1-4 GHz. The radar working frequency is divided into a plurality of wave bands, and the sequence from low to high is as follows: the frequencies of S band, C band, X band and Ku band are usually 2GHz-18 GHz. In the military field, the rapid development of modern radio detection technology and radar detection systems greatly improves the capability of searching and tracking targets in war, so that the threat of traditional combat weapons in war is greater and greater, and therefore, in order to reduce the harm of electromagnetic radiation to human production and living environment, and also in order to ensure military safety, the development and design of high-efficiency electromagnetic protection materials have very important significance to human health and national security.
A wave-absorbing material is a functional material that absorbs or attenuates electromagnetic waves incident on the surface of the material, thereby reducing the radiation of the electromagnetic waves. The wave-absorbing material provides possibility for thoroughly eliminating electromagnetic pollution, the absorption strength and the effective absorption bandwidth are the most important two evaluation indexes of the wave-absorbing material, and besides the absorption strength and the effective absorption bandwidth, the coating thickness of the wave-absorbing material is thin, and the light weight is also a pursued aim. Therefore, the ideal wave absorbing material should meet the requirements of 'strong, wide, thin, light' and the like.
The nano material presents a plurality of singular phenomena and properties which are different from macroscopic objects and single isolated atoms due to quantum effects, locality of substances and huge surface and interface effects, and has important application values in the aspects of electromagnetism, chemical industry, ceramics, optics, biology, medicine and the like. The nano wave-absorbing material has the characteristics of light weight, wide frequency band, good compatibility, thin thickness and the like while having good wave-absorbing performance. However, it is difficult to achieve the multi-band and wide-band absorption effect by a single wave-absorbing material, and the composite wave-absorbing material can enhance the wave-absorbing performance by various wave-absorbing mechanisms so as to achieve a good absorption effect. Therefore, the research and development of nano composite wave-absorbing materials is important. Carbon-based materials are favored by researchers because of their corrosion resistance, high dielectric constant, low density, etc., however, carbon-based materials are non-magnetic and have high conductivity, and the loss mechanism is mainly limited to resistive losses associated with conductivity, and have the disadvantages of poor impedance matching, weak absorption strength, narrow wave absorption frequency band, etc. when used alone. The nano composite material obtained by compounding the carbon material and the metal material has dielectric loss and magnetic loss, and achieves the purpose of reducing the material quality. In addition, the microstructure of the material is a key factor affecting the wave absorbing performance besides the phase composition of the wave absorbing material. For example, the porous structure or high porosity in the material is beneficial to the multiple conduction and dissipation of electromagnetic waves, and meanwhile, the material with the high porosity structure is filled with air, so that the impedance matching of the material is improved, and the wave absorbing performance is improved.
Metal-organic frameworks (Metal-Organic Frameworks, MOFs) are crystalline porous materials with periodic network structures formed by interconnecting inorganic Metal centers (Metal ions or Metal clusters) and bridged organic ligands through self-assembly, and are research hotspots in various fields of material chemistry due to the advantages of ordered and regular structures, structural and functional designability and the like. MOFs can be calcined at high temperature to prepare porous carbon composite materials with ordered structures, and become ideal precursors for preparing various functional nano materials. Because CuO has good wave-transmitting performance, most electromagnetic waves can enter the material; the iron oxide or iron has magnetism, and therefore, the invention aims to obtain the magnetic carbon wave-absorbing composite material by taking a metal organic framework compound (MOFs) formed by combining copper and iron as a precursor and adopting a high-temperature pyrolysis strategy.
The detonation method is firstly used for research and development of nano-diamond, and is popularized to research of various nano-materials, such as nano-graphite, carbon nano-tube, nano-nitride, nano-alumina, manganese ferrite (spinel), synthetic carbon-coated metal nano-material and the like. The explosive explosion chemical reaction is utilized to quickly convert chemical energy into heat energy at the very short explosion moment, and meanwhile, strong shock waves are generated, so that reactants are gasified or form atom clusters, molecular clusters or small-mass active groups, and the active groups such as the atom clusters interact and deposit to form substances with nanoscale dimensions and novel structures in the cooling process (Roning, li Xiaojie teaching, research on synthesizing carbon-coated metal nano materials by a detonation method, university of great company, doctor's treatises, 2011) so that the detonation method is unique in preparation methods of a plurality of nano materials, and has the characteristics of simplicity in operation, high efficiency, economy, energy conservation, environmental protection and the like.
The tetrazole compound has excellent coordination capability and various coordination modes, contains a large number of N= N, C-N bonds with higher enthalpy of formation in the structure, has higher energy, and has most of N combustion products 2 The tetrazole acetic acid does not cause pollution, contains carboxyl, and is a good energetic ligand. Therefore, tetrazoleacetic acid is taken as a ligand, copper and iron are taken as central atoms, and the copper-iron heteronuclear energetic complex { [ Cu ] is prepared II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n The method comprises the steps of placing the material into a stainless steel explosion-proof reaction kettle with a high-temperature resistant and acid-alkali resistant inner container, heating the container to 280-300 ℃ in a furnace to make the energetic copper-iron heteronuclear energetic complex explode and decompose, cooling the exploded and decomposed matter, placing the cooled exploded and decomposed matter into a tubular furnace filled with inert gas, and calcining at different temperatures for a certain time to obtain the nano-micron composite wave absorbing material. After the composite powder and paraffin are mixed according to the mass ratio to form a coaxial ring with the outer diameter of 7.00mm, the inner diameter of 3.04mm and the thickness of 2.00mm, the wave absorbing characteristic of the composite material is tested, and the result shows that when the synthesized powder (calcined at 650 ℃ for 2 hours) has the filling quantity of 70wt%, the effective absorption bandwidth lower than-10 dB is 17.1GHz (0.9-18 GHz) within the range of 0-18GHz and the thickness of 1-10mm, the composite material is a full-band wave absorbing material; when the matching thickness is 1.1mm, the maximum absorption strength reaches-40.1 dB at 16.3GHz, and the composite material is intended to be used as an ultrathin wave-absorbing material, so that the composite material has wide application potential both in civil use and military use, and the synthesis method has the characteristics of mild reaction process, simplicity, rapidness, environmental protection and easiness in industrialization.
Disclosure of Invention
A process for preparing the composite wave-absorbing material by explosion to decompose the energetic metal complex includes such steps as preparing the precursor of energetic copper-iron tetrazole acetate complex, explosion in sealed container, calcining at different temp for a certain time, and high-efficiency preparing porous composite wave-absorbing powder.
The implementation process of the invention is as follows:
1. synthesis of copper-iron tetrazole energetic complex precursors: weighing 1.0-1.2mmol tetrazole acetic acid (Htza) and dissolving in 10.0-12.0mL distilled water, and using 1.0 mol.L -1 The pH of the solution is adjusted to 8.0-9.0 by adding 4.0-6.0mL of CuCl to the solution 2 ·2H 2 O(0.1mol·L -1 ) Stirring at room temperature for 1-2 hr, and then dropwise adding 0.1 mol.L of 4.0-6.0. 6.0mL to the solution -1 Fe (NO) 3 ) 3 Is a solution of (a) and (b). After two or three days, yellow-brown polyhedral crystals are generated. Washing with distilled water, and air drying to obtain copper-iron heteronuclear energetic complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n 。
The above examples are only examples of tetrazole acetic acid and copper chloride, and ferric nitrate is used for synthesizing copper-ferric heteronuclear tetrazole acetic acid complex, the added metal ions should comprise corresponding sulfate, acetate, nitrate, carbonate and the like, and the concentration range of each reactant can be respectively increased and decreased by ten times, and the ratio of the ligand to each metal ion is 12:1-1:12.
2. Precursor { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n Explosive decomposition of (c): heteronuclear energetic complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n (0.5 g) is placed in a small stainless steel explosion-proof reaction kettle (with the inner diameter of 40mm, the height of 90mm, the temperature resistance of Gao Wen ℃ and the pressure resistance of less than or equal to 6 MPa) with a liner (30 mL, the temperature resistance of Gao Wen ℃) of which the inner container is a high temperature resistant and acid-base resistant para-polyphenol (PPL), then the container is placed in a muffle furnace for 5-10 ℃ for min -1 Heating to 280-300 deg.c to decompose the energetic copper-iron heteronuclear complex, stopping heating and cooling to room temperature.
3. Preparation of the composite wave absorber: cooling the precursor explosive decomposition product, placing in a tube furnace filled with nitrogen or argon at a ratio of 5-10℃·min -1 The temperature is raised to a certain temperature from room temperature, and then the calcination is carried out for 2-3 hours, and the temperature is lowered to room temperature, so that the nano-micron composite wave-absorbing material can be prepared.
4. And (3) curing and forming with paraffin: fully mixing the products calcined for 2-3 hours at different temperatures with paraffin according to a certain mass ratio, putting the mixture into an oven at 80 ℃ for heating for about 20 minutes, taking out the mixture after the paraffin becomes a liquid state, and rapidly and uniformly stirring the mixture; after the sample is solidified, the sample is continuously placed into an oven at 80 ℃ for heating for 20min, and then is taken out and continuously stirred uniformly, and the process is repeated for three times. And placing the uniformly stirred sample into a mould, taking a fixed pressure, pressing into a circular ring, controlling the thickness of the sample to be 2.000+/-0.020 mm, and testing the wave absorbing performance of the sample.
Compared with the prior art, the nano-scale and micron-scale wave-absorbing material is prepared by utilizing an energetic material explosion method, and the method has the characteristics of high yield, low density, environmental protection and simplicity, and the performance of the obtained product is superior to that of the wave-absorbing material obtained by the traditional method. Studies have shown that: under inert atmosphere, different calcining temperatures have different influences on the wave absorbing performance of the composite material: when the calcining temperature is 650 ℃, the ratio of the composite powder and paraffin wax which are preserved for 2 hours is 7:3, the effective absorption bandwidth which is lower than-10 dB is 17.1GHz (0.9-18 GHz) within the range of 0-18GHz and the thickness of 1-10mm, and the composite powder is a near full-wave microwave absorbing material.
Drawings
FIG. 1{ [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n A three-dimensional network and topology structure diagram a;
FIG. 2{ [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n A three-dimensional network and topology structure b;
FIG. 3{ [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n A three-dimensional network and topology structure c;
FIG. 4 XRD pattern of explosive decomposition product calcined in nitrogen atmosphere at 550℃for 2 hours in example 1;
FIG. 5 is a graph a of the reflection loss of electromagnetic waves with frequency for the composite wave absorbing material obtained in example 1 at different thicknesses;
FIG. 6 is a graph b of the reflection loss of electromagnetic waves with frequency at different thicknesses of the composite wave-absorbing material obtained in example 1;
FIG. 7 is an XRD pattern of a wave-absorbing powder obtained by calcining at 650℃for 2 hours in example 2;
FIG. 8 is a graph a of the electromagnetic wave reflection loss of the composite powder obtained in example 2 with frequency variation at different thicknesses;
FIG. 9 is a graph b of the electromagnetic wave reflection loss of the composite powder obtained in example 2 with frequency variation at different thicknesses;
FIG. 10 is an XRD pattern of the wave-absorbing powder obtained by calcining at 750℃for 2 hours in example 3;
FIG. 11 is a graph a showing the variation of the reflection loss of electromagnetic waves with frequency at different thicknesses of the composite wave-absorbing material obtained in example 3;
FIG. 12 is a graph b of the reflection loss of electromagnetic waves with frequency at different thicknesses of the composite absorbing material obtained in example 3;
FIG. 13 is a Raman diagram showing the calcination of the explosion decomposed product at 550 ℃,650 ℃ and 750 ℃ for 2h of the wave-absorbing powder, respectively;
FIG. 14 is an SEM image a of porous wave-absorbing powder obtained by calcination at 650 ℃ for 2 h;
FIG. 15 is an SEM image b of porous wave-absorbing powder obtained by calcination at 650℃for 2 h;
FIG. 16 is a graph showing the change in dielectric loss and magnetic loss tangent of a sample at a calcination temperature of 550 ℃;
FIG. 17 is a graph of impedance match versus frequency for a sample at 550℃calcination temperature;
FIG. 18 is a graph showing the variation of dielectric loss and magnetic loss tangent of a sample at a calcination temperature of 650 ℃;
FIG. 19 is a graph of impedance match versus frequency for a sample at a calcination temperature of 650 ℃;
FIG. 20 is a graph showing the change in dielectric loss and magnetic loss tangent of a sample at a calcination temperature of 750 ℃;
FIG. 21 is a graph of impedance match versus frequency for a sample at a calcination temperature of 750deg.C;
Detailed Description
The invention will be further illustrated with reference to specific examples. The following examples are only illustrative of the present invention and are not intended to limit the scope of the invention.
Example 1
The preparation method of the composite wave-absorbing material based on tetrazole copper acetate-iron complex comprises the following steps:
1) 0.1536g (1.2 mmol) of tetrazoleacetic acid (Htza) was dissolved in 12mL of distilled water, and 1.0 mol.L was used -1 Adjusting the pH of the solution to 9.0 by adding CuCl to the solution 2 ·2H 2 O (0.1023 g,0.6 mmol), after stirring at room temperature for 1 hour, 6.0mL of 0.1 mol.L was added dropwise to the solution -1 Fe (NO) 3 ) 3 Is a solution of (a) and (b). After two days, yellowish-brown polyhedral crystals were formed. Washing with distilled water, and air drying to obtain copper-iron heteronuclear energetic complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n 。
2) Precursor { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n Explosion decomposition of: heteronuclear energetic complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n (0.5 g) is placed in a small-sized stainless steel explosion-proof reaction kettle with a high temperature resistant acid-base resistant liner, and the container is placed in a muffle furnace for 5 ℃ and min -1 Is heated to 280 ℃, and is cooled to room temperature along with the furnace after the energetic copper-iron heteronuclear energetic complex is decomposed by explosion.
3) Preparation of the composite wave absorber: cooling the precursor explosive decomposition product, placing in a tube furnace filled with nitrogen gas at 5 deg.C for min -1 Is heated to 550 ℃ from room temperature, and is calcined by heat preservationAnd (3) burning for 2 hours, and then cooling to room temperature, so as to prepare the composite wave-absorbing material.
4) And (3) curing and forming with paraffin: and fully mixing the product and paraffin according to the mass ratio of 7:3 under the calcination at the temperature, then placing the mixture into an oven at 80 ℃ for heating for about 20min, taking out the mixture after the paraffin becomes a liquid state, rapidly stirring the mixture uniformly, continuously placing the mixture into the oven at 80 ℃ for heating for 20min after the sample is solidified, taking out the mixture, continuously stirring the mixture uniformly, and repeating the steps for three times. Obtaining the composite wave-absorbing material.
As can be seen from fig. 1-3: the copper-iron complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n Belongs to orthorhombic system, P6 3 /m space group. It is made up of [ Fe 3 O(tza) 6 ] + And Cu 2+ An infinite three-dimensional network structure is formed. Its asymmetric structural unit includes one [ Fe 3 O(tza) 6 ] + Cation unit, one Cu (II) ion, two NO 3 - Ions, one Cl - Ions, three are formulated as water and four lattice water molecules.
As can be seen from FIG. 4, the wave-absorbing powder obtained in example 1 (CuFe-MOF-550) was a mixture, and diffraction peaks at 2θ=30.2°, 35.5 °, 43.4 °, 57.1 ° and 62.6 ° were compared with Fe 3 O 4 Standard diffraction cards (COD No. 96-900-5813) respectively correspond to Fe 3 O 4 The crystal plane diffraction peaks of (022), (113), (004), (115), (044); diffraction peaks at 2θ=30.2 °, 35.5 °, 43.4 °, 57.1 °, 62.6 °, 74.1 ° contrast CuFe 2 O 4 Standard diffraction cards (COD No. 96-901-2842) respectively correspond to CuFe 2 O 4 The crystal plane diffraction peaks of (022), (113), (004), (115), (044), (335); diffraction peaks at 2θ=41.2 °, 48.0 °, 70.2 °, 84.7 ° contrast Fe 4 N standard diffraction cards (COD No. 96-900-4226) correspond to Fe respectively 4 Crystal plane diffraction peaks of (111), (002), (022), (113) of N; the diffraction peaks at 2θ=43.4 °, 50.6 °, 74.2 ° are consistent with the crystal plane diffraction peaks of (111), (002), (022) of Cu against the standard diffraction card of Cu (COD No. 96-901-3015). Description of calcining at 550 ℃The main component of the firing product, namely the composite material, is Fe 3 O 4 ，Fe 4 N，Cu，CuFe 2 O 4 The composition is formed. As can be seen from FIG. 13, the product obtained by calcining at 550℃has two distinct characteristic peaks, each at 1350cm -1 And 1590cm -1 Nearby, two characteristic peaks, D and G, I, attributed to the carbon material D /I G The values of (2) represent the defect degree and graphitization degree of the material itself, and the intensity ratio of the D peak and the G peak of CuFe-MOF-550 (I D /I G ) The value of (2) is 1.03.I D /I G The smaller the value, the greater the degree of graphitization of the sample and the smaller the defects. The defect is caused by the escape of lattice disorder vibration from the center of Brillouin zone, and is represented by the occurrence of D peak, while G peak is caused by sp of carbon atom 2 Vibrations in the plane of the track. In combination, the CuFe-MOF-550 powder is made of Fe 3 O 4 ，Fe 4 N，Cu，CuFe 2 O 4 Amorphous carbon and graphene.
FIGS. 5 and 6 show the electromagnetic parameters of the powder product and paraffin wax in a mass ratio of 7:3, which were pressed in a special mold to form a coaxial sample (S1) with an outer diameter of 7.00mm, an inner diameter of 3.04mm and a thickness of about 2mm, and the electromagnetic parameters were measured by a vector network analyzer model Agilent E5071C, and the wave-absorbing performance graph was calculated, with the test frequency ranging from 0 to 18GHz. The reflection loss of sample S1 is plotted as a function of frequency as shown in FIG. 5, and the maximum absorption strength reaches-5.3 dB at 1.0GHz when the matching thickness is 5.5 mm; when the matching thickness is 10mm, the maximum absorption strength reaches-5.8 d at 0.4GHz, as shown in FIG. 6. The results demonstrate that the composite material obtained under this condition has poor wave-absorbing properties.
Example 2
The preparation method and the steps of the wave-absorbing material prepared based on the tetrazole copper-iron acetate complex are the same as those of example 1. The main difference is that the calcination temperatures are different in a nitrogen-filled tube furnace, in this case 5 ℃ min -1 The temperature is raised from room temperature to 650 ℃, the temperature is kept for 2 hours, and then the temperature is lowered to room temperature, so that the nano-micron composite wave-absorbing material (expressed by S2) is obtained.
As can be seen from fig. 7, the sample of example 2 (CuFe-MOF-650) was prepared at 2θ=18.3 °, 30.2 °, 37.3 °, 43Diffraction peaks at 4 °, 57.1 °, 62.7 °, 74.2 ° contrast Fe 3 O 4 Standard diffraction cards (COD No. 96-900-2319) of (A) correspond to Fe respectively 3 O 4 The diffraction peaks of (111), (022), (222), (004), (115), (044), (335) indicate Fe in the product 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Diffraction peaks at 2θ=41.2 °, 48.0 °, 70.2 °, 84.7 ° and Fe 4 The characteristic diffraction peaks of the standard diffraction card of N (COD No. 96-900-4226) are almost identical and correspond to Fe respectively 4 The diffraction peaks of the crystal faces (111), (002), (022) and (113) of N show that Fe exists in the product 4 N; diffraction peaks at 2θ=43.4 °, 50.6 °, 74.2 ° against the standard diffraction card of Cu (COD No. 96-901-2955), respectively corresponding to the (111), (002), (022) crystal plane diffraction peaks of Cu, indicating Cu in the product; diffraction peaks at 2θ=30.2 °, 35.6 °, 43.4 °, 57.1 °, 62.7 °, 74.2 ° contrast CuFe 2 O 4 Standard diffraction cards (COD No. 96-901-2439) respectively correspond to CuFe 2 O 4 The diffraction peaks of (022), (113), (004), (115), (044), (335) indicate CuFe in the product 2 O 4 Is present. FIG. 13 shows that the calcined product at 650℃has two distinct characteristic peaks, each at 1350cm -1 And 1590cm -1 Nearby, two characteristic peaks, D and G, I, attributed to the carbon material D /I G The magnitude of the value of (c) indicates the magnitude of the defect degree and graphitization degree of the material itself, and the ratio of the intensities of the D peak and the G peak of CuFe-MOF-650 (I D /I G ) Has a value of 1.01, compared with I in example 1 D /I G The small size indicates that the graphitization degree of the sample is increased and the defect degree is reduced. In summary, the calcined product at 650 ℃ is mainly Fe 3 O 4 ，Fe 4 N，Cu，CuFe 2 O 4 Amorphous carbon and graphene.
As can be seen from fig. 14 and 15: the S2 wave absorbing material is in a porous structure and is a nano-micron aggregate with uniform size, and the wave absorbing material with the porous structure is favorable for multiple reflection and absorption of incident electromagnetic waves in the material and can show good wave absorbing performance. FIG. 5 is a graph showing the variation of reflection loss with frequency of a sample obtained by calcining at 650℃for 2 hours, and when the matching thickness is 1.1mm, as can be seen from FIG. 8, the maximum absorption intensity reaches-40.1 dB at 16.3GHz, and the effective absorption (. Ltoreq.10 dB) frequency bandwidth reaches 3.2GHz. The powder can be used as an ultrathin wave absorber of the wave band. As can be seen from FIG. 9, at a frequency of 1.0GHz and a matching thickness of 10mm, the minimum reflection loss reaches-16.4 GHz. And the peak value of the reflection loss moves to low frequency along with the increase of the thickness, the effective absorption bandwidth lower than-10 dB is 17.1GHz (0.9-18 GHz) within the range of 0-18GHz and the thickness is 1-10mm, so that the composite powder is expected to be a wave-absorbing material with potential for civil use and military use.
Example 3 the process was the same as in example 1, the powder after explosive decomposition of the precursor was placed in a tube furnace filled with nitrogen at 5℃min -1 The temperature is raised to 750 ℃ from room temperature, the calcination is carried out for 2 hours, and then the temperature is lowered to room temperature, so that the composite wave-absorbing material is prepared (S3). S3 and paraffin were thoroughly mixed in the same mass ratio (7:3) as in example 1, and under the same preparation conditions, a composite wave-absorbing material (S3) was produced.
FIG. 10 is a graph showing diffraction peaks at 2θ=30.2°, 35.5 °, 43.4 °, 57.1 °, 62.7 °, 74.2 ° for the sample of example 3 (CuFe-MOF-750, S3) corresponding to Fe 3 O 4 The diffraction peaks of (022), (113), (004), (115), (044), (335) of the standard diffraction card (COD No. 96-900-5813) indicate Fe in the product 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Diffraction peaks at 2θ=41.2 °, 48.0 °, 70.2 °, 84.7 ° correspond to Fe 4 The diffraction peaks of the crystal planes (111), (002), (022) and (113) of the standard diffraction card (COD No. 96-900-4226) of N show that Fe exists in the product 4 N; diffraction peaks at 2θ=43.4 °, 50.6 °, 74.2 ° correspond to the (111), (002), (022) crystal plane diffraction peaks of the standard diffraction card of Cu (COD No. 96-901-3015), respectively, indicating Cu in the product. Diffraction peaks at 2θ=44.7 °, 65.1 °, 82.4 ° correspond to (011), (002), (112) crystal plane diffraction peaks of the standard diffraction card (COD No. 96-900-6588) of Fe, respectively, indicating Fe in the product. As can be seen from FIG. 13, the calcined product at 750℃has two distinct characteristic peaks, each at 1350cm -1 And 1590cm -1 Nearby, two being of carbon materialCharacteristic peaks D and G, I D /I G Has a value of 1.00, I at three different calcination temperatures D /I G The minimum value indicates the greatest degree of graphitization of the sample. In conclusion, the main component of the calcined product at 750 ℃ is Fe 3 O 4 ，Fe 4 N, fe, cu, amorphous carbon and graphene.
Fig. 11 and 12 are reflectance spectra of electromagnetic waves with frequency change under different thicknesses of the composite wave-absorbing material S3 prepared in example 3. At a temperature of 750 ℃, when the matching thickness is 1.5mm and 5.5mm, the minimum reflection loss can reach-9.3 dB (frequency is 12.2 GHz) and-9.6 dB (frequency is 2.1 GHz), which are close to-10 dB respectively. At 1.9GHz, the minimum reflection loss reaches-9.7 dB and approaches-10 dB under the condition of 6.0mm in thickness.
FIGS. 16, 18 and 20 show the values of the dielectric loss and the magnetic loss tangent as a function of frequency at three different temperatures, and it can be seen from the figures that CuFe-MOF-550, cuFe-MOF-650 and CuFe-MOF-750 have values of the magnetic loss tangent (tan. Delta.) in the frequency range of 0 to 18.0GHz μ ) Above the dielectric loss tangent (tan delta) ε ) The magnetic loss mechanism is dominant. When the material surface matches the impedance of free space, i.e. impedance match value (|Z) 0 /Z in I) is close to 1.0, the electromagnetic wave can reduce reflection, and the electromagnetic wave is maximally incident into the material, so as to obtain maximum attenuation. As can be seen from fig. 17, 19, 21: the CuFe-MOF-650 has the largest impedance matching value at the frequency of 17.7GHz and the thickness of 1.0mm, is close to 1.0, and has wave absorbing performance stronger than that of the samples CuFe-MOF-550 and CuFe-MOF-750. Therefore, after the precursor is exploded in an explosion-proof reaction kettle, calcining the precursor in a tube furnace at 650 ℃ for 2 hours to obtain powder with the thickness of 1-10mm and the effective absorption bandwidth of 17.1GHz (0.9-18 GHz) which is lower than-10 dB in the range of 0-18GHz, which is a near-full-wave-band wave-absorbing material; when the matching thickness is 1.1mm, the maximum absorption strength reaches-40.1 dB at 16.3GHz, and the CuFe-MOF-650 powder has potential of being used as an ultrathin wave-absorbing material, and in a word, the CuFe-MOF-650 powder has wide application prospect both for civil use and for military use.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (3)
1. A composite wave absorber based on tetrazole copper-iron acetate complex derivative is characterized in that the composite wave absorber is prepared from Fe 3 O 4 、 Fe 4 N、Cu、CuFe 2 O 4 The preparation method of the nano-scale and micron-scale composite powder composed of amorphous carbon and graphene comprises the following steps: step (1), 1.0 to 1.2mmol of organic ligand tetrazole acetic acid (Htza) is weighed and dissolved in 10.0 to 12.0. 12.0mL of distilled water, and 1.0 mol.L is used -1 The pH of the solution was adjusted to 8.0-9.0 by NaOH, and 0.1 mol.L was added to the solution -1 CuCl 2 ·2H 2 O4.0-6.0 mL, stirring at room temperature for 1-2 hr, and dropwise adding 0.1 mol.L of 4.0-6.0mL -1 Fe (NO) 3 ) 3 After two or three days, yellow-brown polyhedral crystals are generated, and distilled water is used for cleaning and air drying to obtain the copper-iron heteronuclear energetic complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n The method comprises the steps of carrying out a first treatment on the surface of the Step (2), 0.5g copper-iron heteronuclear energetic complex { [ Cu ] II Fe III 3 O(tza) 6 (H 2 O) 3 ]·Cl·(NO 3 ) 2 ·4H 2 O} n Placing in a small stainless steel explosion-proof reaction kettle with a high temperature resistant and acid and alkali resistant liner, and then placing the reaction kettle in a muffle furnace at 5-10deg.C for min -1 Is heated to a rate of 280 to 300 o C, enabling the energetic copper-iron heteronuclear energetic complex to be subjected to explosive decomposition to obtain explosive decomposition products, and cooling the explosive decomposition products to room temperature along with a furnace; step (3), placing the explosive decomposer cooled to room temperature in the step (2) in a tube furnace filled with inert gas at a temperature of 5-10 ℃ for min -1 Respectively, from room temperature to 550 o C，650 o C and 750 o Calcining for 2-3h under the condition C, and then cooling to room temperature.
2. The tetrazolium copper-iron acetate complex-based derivative composite wave absorber according to claim 1, wherein said CuCl is in step (1) of the preparation method thereof 2 ·2H 2 O and Fe (NO) 3 ) 3 Can be replaced by corresponding sulfate, nitrate, acetate and chloride; the concentration range of each reactant can be increased and decreased by ten times, and the ratio of the ligand to each metal ion is 12:1-1:12.
3. The composite wave absorber derived from tetrazolium copper-iron acetate complex according to claim 1, wherein the inert gas in step (3) of the preparation method is nitrogen, argon or a mixture thereof.
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